Azo dyes with an acetalized diazo component of the thiophene or thiazole series

ABSTRACT

Azo dyes of the formula ##STR1## where L 1 , L 2 , L 3 , L 4 , X and K are as defined in the specification, and crystal forms of thienylazobenzene dyes are useful for dyeing or printing textile materials such as polyesters, fibers or fabrics made of cellulose esters or polyamides or blend fabrics from polyester and cellulose fibers with high color strength, good fastness properties and brilliant hues.

This is a Division of application Ser. No. 08/307,794 filed on Sep. 30, 1994, now U.S. Pat. No. 5,466,790 which was filed as International Application No. PCT/EP93/01043 on Apr. 30, 1993.

The present invention relates to novel azo dyes of formula I ##STR2## where L¹ is hydrogen, C₁ -C₈ -alkyl or phenyl,

L² and L³ are identical or different and each is independently of the other C₁ -C₈ -alkyl, which may be substituted and may be interrupted by 1 or 2 oxygen atoms in ether function, or together are a radical of the formula ##STR3## where n is 0, 1 or 2, Y¹ and Y⁴ are identical or different and each is independently of the other hydrogen, hydroxymethyl, 1,2-dihydroxyethyl or a radical of the formula COO⊖M⊕ or SO₃ ⊖M⊕, Y² and Y³ are identical or different and are each independently of the other halogen or hydroxymethyl, and M⊕ is the equivalent of a cation,

L⁴ is hydrogen, C₁ -C₈ -alkyl, which may be interrupted by 1 or 2 oxygen atoms in ether function and may be substituted, substituted or unsubstituted phenyl, halogen, C₁ -C₈ -alkoxy, substituted or unsubstituted phenoxy, C₁ -C₈ -alkylthio, C₁ -C₈ -alkylsulfonyl, substituted or unsubstituted phenylthio, substituted or unsubstituted phenylsulfonyl, C₁ -C₈ -alkoxycarbonyl, C₃ -C₆ -alkenyloxycarbonyl or phenoxycarbonyl,

X is nitrogen or the radical C-L⁵, where L⁵ is cyano, C₁ -C₈ -alkoxycarbonyl, C₃ -C₆ -alkenyloxycarbonyl, phenoxycarbonyl, C₁ -C₈ -alkanoyl, benzoyl, carbamoyl, mono- or di(C₁ -C₄ -alkyl)carbamoyl, phenylcarbamoyl, C₁ -C₈ -alkylsulfonyl or substituted or unsubstituted phenylsulfonyl, and

K is the radical of a coupling component,

to novel crystal forms of thienylazobenzene dyes and to the use of said dyes for dyeing or printing textile materials.

DE-A-3 529 831, GB-A-2 071 684, DE-A-2 818 101, EP-A-362 637, DE-A-3 906 066, EP-A-201 896 and EP-A-390 666 disclose azo dyes which are similar to those of the formula I. They have a carbonyl group in ring position 5 of the thiophene or thiazole ring. It has been found that the solubility of these dyes leaves something to be desired. Nor is their application property profile satisfactory in every respect.

It is an object of the present invention to provide novel azo dyes which are free of the above-mentioned defects.

We have found that this object is achieved by the azo dyes of the formula I defined at the beginning.

In the azo dyes of the formula I, K can be for example the radical of a coupling component of the aniline, aminothiazole, pyrazole, diaminopyridine, hydroxypyridone or quinoline series.

Emphasis is given to azo dyes of the formula I where K is a radical of the formula ##STR4## where R¹ and R² are identical or different and each is independently of the other hydrogen, substituted or unsubstituted C₁ -C₈ -alkyl, which may be interrupted by 1 or 2 oxygen atoms in ether function, C₅ -C₇ -cycloalkyl or C₃ -C₆ -alkenyl, which may be substituted by halogen, in particular by chlorine or bromine,

R³ is hydrogen, C₁ -C₈ -alkyl or C₁ -C₈ -alkoxy,

R⁴ is hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₈ -alkylsulfonylamino, substituted or unsubstituted C₁ -C₈ -alkanoylamino or benzoylamino,

R⁵ is hydrogen, C₁ -C₈ -alkyl, substituted or unsubstituted phenyl or thienyl,

R⁶ is amino or hydroxyl,

R⁷ is C₁ -C₈ -alkyl, which may be interrupted by 1 or 2 oxygen atoms in ether function, benzyl, C₅ -C₇ -cycloalkyl, C₃ -C₆ -alkenyl or substituted or unsubstituted phenyl

R⁸ is hydrogen or C₁ -C₈ -alkyl,

R⁹ is cyano, carbamoyl or acetyl,

R¹⁰, R¹¹ and R¹² are identical or different and each is independently of the others substituted or unsubstituted C₁ -C₈ -alkyl which may be interrupted by 1 or 2 oxygen atoms in ether function, C₅ -C₇ -cycloalkyl, substituted or unsubstituted phenyl, C₃ -C₆ -alkenyl, substituted or unsubstituted benzoyl, C₁ -C₈ -alkanoyl, C₁ -C₈ -alkylsulfonyl or substituted or unsubstituted phenylsulfonyl, or R¹¹ and R¹² are together with the nitrogen atom joining them together a 5- or 6-membered saturated heterocyclic radical, which may contain further hereto atoms, and

R¹³ is hydrogen or C₁ -C₈ -alkyl.

Any alkyl or alkenyl appearing in the abovementioned formulae may be straight-chain or branched.

Any substituted phenyl appearing in the abovementioned formulae may have as substituents for example C₁ -C₄ -alkyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl, carboxyl or hydroxysulfonyl. The number of substituents in substituted phenyl is in general from 1 to 3.

Any substituted alkyl appearing in the abovementioned formulae may have as substituents for example hydroxyl, halogen, cyclohexyloxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoyloxy, hydroxysulfonyl, cyano, cyclohexyl or substituted or unsubstituted phenyl. The number of substituents in substituted alkyl is in general from 1 to 3.

L¹, L², L³, L⁴, R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R¹⁰, R¹¹, R¹² and R¹³ are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl or 2-ethylhexyl.

L⁴ may also be for example methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, phenylthio, 2-methylphenylthio, 2-methoxyphenylthio, 2-chlorophenylthio, fluorine, chlorine, bromine, phenoxy, 2-methylphenoxy, 2-methoxyphenoxy, 2-chlorophenoxy, phenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl or 2-, 3- or 4-methoxyphenyl.

L⁴, R³ and R⁴ may also be for example methoxy, ethoxy, propoxy, isoproproxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tertpentyloxy, hexyloxy, 2 -methylpentyloxy, heptyloxy, octyloxy, isooctyloxy or 2 -ethylhexyloxy.

L¹⁵ may also be for example, like L⁴, R¹⁰, R¹¹ and R¹² methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, phenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl or 2-chlorophenylsulfonyl.

L⁴ and L⁵ may also be for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, prop-2-en-1-yloxycarbonyl, 2-methylprop-2-en-1-yloxycarbonyl, but-2-en-1-yloxycarbonyl or but-3-en1-yloxycarbonyl.

R¹, R², R¹¹, R¹² and R¹³ may also be for example cyclopentyl, cyclohexyl or cycloheptyl.

L⁵ may also be for example formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.

L¹, L², L⁴, R¹, R², R¹⁰, R¹¹ and R¹² may also be for example 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-isobutoxyethyl, 2- or 3-methoxypropyl, 1-methoxyprop-2-yl, 2- or 3-ethoxypropyl or 2- or 3-propoxypropyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 1-hydroxyprop-2-yl, 2- or 4-hydroxybutyl, 3-hydroxybut-2-yl, trifluoromethyl, 2-chloroethyl, 2- or 3-chloropropyl, 2-cyclohexyloxyethyl, 2- or 3-cyclohexyloxypropyl, 2- or 4-cyclohexyloxybutyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 2-formyloxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2- or 3-acetyloxypropyl, 2- or 4-acetyloxybutyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 3 -ethoxycarbonylpropyl, 2- or 3-butoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 4-cyanobutyl, 2-cyclohexylethyl, 2- or 3-cyclohexyl-propyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonyl-propyl, benzyl, 1- or 2-phenylethyl, carboxybenzyl, 1- or 2-carboxyphenylethyl, hydroxysulfonylbenzyl, 1- or 2-hydroxysulfonylphenylethyl, methoxycarbonylbenzyl, 1- or 2-methoxycarbonylphenylethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2- or 3-acetyloxypropyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl or 3-chloroprop-2-en-1-yl.

R¹¹ combined with R¹² and the nitrogen atom joining them together to form a five- or six-membered saturated heterocyclic radical, which may contain further hetero atoms, can be for example pyrrolidinyl, piperidinyl, morpholinyl, thiormorpholinyl, thiomorpholinyl S,S-dioxide, piperazinyl or N-(C₁ -C₄ -alkyl)piperazinyl, such as N-methyl- or N-ethyl-piperazinyl.

L² combined with L³ to form the radical of the formula ##STR5## can be for example: ##STR6## M⊕ is the equivalent of a cation. Suitable cations are metal ions. Metal ions are in particular the ions of lithium, of sodium or of potassium.

Emphasis is given here to sodium and potassium ions, of which sodium ions are particularly important.

Preference is given to azo dyes of the formula I where

L¹ is hydrogen or C₁ -C₈ -alkyl,

L⁴ is substituted or unsubstituted phenyl, halogen or C₁ -C₈ -alkoxy, and

X is nitrogen or the radical C-L⁵, where L⁵ is cyano or C₁ -C₈ -alkoxycarbonyl.

Preference is also given to azo dyes of the formula I where L² and L³ are each independently of the other unsubstituted or hydroxyl-substituted C₁ -C₈ -alkyl, or L² and L³ are together a radical of the formula ##STR7## where Y¹ and Y² are each as defined above.

Preference is further given to azo dyes of the formula I where K is the radical of a diazo component of the aniline series, in particular a radical of the formula IIa.

Particular preference is given to azo dyes of the formula I where

L¹ is hydrogen or C₁ -C₄ -alkyl,

L⁴ is chlorine, bromine or C₁ -C₄ -alkoxy, and

X is nitrogen or the radical C-L⁵ where L⁵ is cyano or C₁ -C₄ -alkoxycarbonyl.

Particular preference is further given to azo dyes of the formula I where

L² and L³ are each independently of the other C₁ -C₄ -alkyl or together a radical of the formula ##STR8##

Particular preference is further given to azo dyes of the formula I where K is a radical of the formula IIa where

R¹ and R² are each independently of the other C₁ -C₄ -alkyl, which may be interrupted by 1 oxygen atom in ether function and may hydroxyl-, cyano- or C₁ -C₄ -alkanoyloxy-substituted, C₃ -C₄ -alkenyl, which may be substituted by chlorine, or else in the case of R¹ hydrogen,

R³ is hydrogen, and

R⁴ is C₁ -C₄ -alkanolylamino, whose alkyl chain may be interrupted by an oxygen atom in ether function.

Very particular emphasis is given to azo dyes of the formula Ia ##STR9## where Q¹ and Q² are each independently of the other C₁ -C₄ -alkyl or a radical of the formula ##STR10## Q³ is chlorine, X is nitrogen or the radical C--CN,

Q⁴ is acetyl, propionyl or methoxyacetyl, and

Q⁵ and Q⁶ are each independently of the other C₁ -C₄ -alkyl, which may be interrupted by an oxygen atom in ether function and may be hydroxyl-, cyano- or acetyloxy-substituted, prop-2-en-1-yl or 3-chloro-prop-2-en-1-yl, or else in the case of Q⁵ hydrogen.

The dyes of the formula I of the invention can be obtained in a conventional manner. One possibility is for example to acetalize a carbonylazo dye of the formula IV ##STR11## where L¹, L⁴, X and K are each as defined above, with a hydroxy compound of the formula Va, Vb, Vc or Vd ##STR12## where L², L³, Y¹, Y², Y³, Y⁴, M⊕ and n are each as defined above, under acid catalysis in the presence or absence of an inert solvent, for example toluene.

Those azo dyes of the formula I of the invention that are free of hydroxysulfonyl groups are advantageously useful as disperse dyes for dyeing or printing textile fibers or fabrics, in particular polyesters, but also fibers or fabrics made of cellulose esters or polyamides or blend fabrics from polyester and cellulose fibers.

To obtain an advantageous color buildup it can be of advantage in some cases to use mixtures between the dyes of the formula I.

The novel azo dyes are notable for high color strength, good fastness properties and brilliant hues.

The azo dyes of the invention are also advantageously useful for thermal transfer from a transfer sheet to plastic-coated paper by means of an energy source (see for example EP-A-416 434).

If acidic dyeing liquors are employed, the acetalized azo dyes of the formula I can also be used with advantage as intermediates for the dyeing of textile fibers or fabrics with the carbonylazo dyes of the formula IV.

This is because the presence of acid in the aqueous dyeing liquor hydrolyzes the acetal group of dye I to form the carbonyl group of the dye of the formula IV.

This technique is particularly advantageous compared with the carbonylazo dyes of the formula IV, since the novel dyes of the formula I are more soluble and thus make it possible to distinctly reduce in the finished dye product the proportion of the frequently slow-to-biodegrade dispersant.

It is also possible to use the novel dyes of the formula I as intermediates for purifying the carbonylazo dyes of the formula IV by acetalizing a carbonylazo dye IV and subsequently hydrolyzing the acetal group.

This method is particularly favorable with the dyes of the formula Ia. The dyes obtained have a brilliance when dyed up that is otherwise obtained only with anthraquinone dyes.

The present invention further provides novel crystal forms of each of the dyes of the formulae IIIa, IIIb and IIIc ##STR13## which crystal forms have the following X-ray diffraction diagrams (Cu--K_(g) radiation):

IIIa)

lines of high intensity at diffraction angles Θ °! of 8.497 and 9.175;

lines of medium intensity at diffraction angles Θ °! of 7.018, 11.836 and 9.721;

lines of low intensity at diffraction angles Θ °! of 25.164, 5.920, 25.934, 24.425, 23.442, 26.335, 13.119, 17.906, 15.674, 13.963, 15.153, 27.471, 14.630, 17.028, 18.833, 20.982, 28.275, 21.247, 19.490, 29.898, 30.726 and 34.570;

IIIb)

lines at high intensity at diffraction angles Θ °! of 24.971 and 12.551;

lines of medium intensity at diffraction angles Θ °! of 22.850 and 11.093;

lines of low intensity at diffraction angles Θ °! of 11.548, 9.100, 27.564, 29.233, 17.967, 7.424, 22.255, 30.296, 28.175, 13.645, 14.406, 17.368, 26.458, 16.018, 16.809, 19.206, 20.006, 32.464, 34.775, 33.479 and 33.833;

IIIc)

lines of high intensity at diffraction angles Θ °! of 7.441;

lines of medium intensity at diffraction angles Θ °! of 11.090;

lines of low intensity at diffraction angles Θ °! of 8.662, 10.063, 26.181, 17.373, 19.540, 22.901, 14.950, 12.888, 14.097, 15.961, 28.237, 27.752, 29.035, 32.108, 34.326, 33.239 and 33.543.

The prior art crystal forms of the dyes III, IIIb and IIIc have the following X-ray diffraction diagrams (Cu--K_(g) radiation):

IIIa)

lines of high intensity at diffraction angles Θ °! of 7.472;

lines of medium intensity at diffraction angles Θ °! of 25.805 and 9.085;

lines of low intensity at diffraction angles Θ °! of 11.884, 12.523, 10.798, 5.911, 17.383, 15.967, 23.471, 28.185, 21.610, 28.487, 19.189, 29.894, 20.509 and 32.133;

IIIb)

lines of high intensity at diffraction angles Θ °! of 12.051;

lines of medium intensity at diffraction angles Θ °! of 9.100, 24.408, 25.772, 7.406, 13.393, 28.145, 8.194, 6.922 and 6.435;

lines of low intensity at diffraction angles Θ °! of 20.626, 14.420, 15.198, 21.433, 16.128, 17.635, 18.236, 30.787, 31.882, 33.865 and 34.834;

IIIc)

lines of high intensity at diffraction angles Θ °! of 26.470, 9.671, 11.277 and 25.759;

lines of medium intensity at diffraction angles Θ °! of 7.341, 8.449, 7.750, 10.755, 14.441, 24.870 and 27.019;

lines of low intensity at diffraction angles Θ °! of 12.715, 23.160, 21.288, 16.613, 21.531, 17.954, 22.268, 21.872, 19.583, 30.530, 32.342 and 32.958.

The X-ray diffraction diagrams were each recorded using a powder diffractometer of type D 5000 from Siemens.

The novel crystal forms of the dyes IIIa, IIIb and IIIc produce dyeings of very high brilliance on textile fibers or fabrics.

Embodiments of the invention will now be more particularly described by way of example.

EXAMPLE 1

240 g of the compound of the formula I ##STR14## were refluxed in 2 l of methanol for 8 hours. After cooling the precipitate was filtered off with suction and dried under reduced pressure. The dye thus obtained had the formula ##STR15## and was recrystallized from 1 l of toluene.

Yield: 160 g; melting point: 138° C.; λ_(max) (in acetone): 562 nm (ε=55000).

EXAMPLE 2

20 g of the compound of the formula ##STR16## were refluxed in 500 ml of methanol for 4 hours. After cooling the residue was filtered off with suction at room temperature and the filtrate was admixed with 100 ml of water. The precipitated dye of the formula ##STR17## was filtered off with suction and dried.

Yield: 18.2 g; melting point: 140° C.; λ_(max) (in acetone): 551 nm (ε=46000).

EXAMPLE 3

7.5 g of the compound of the formula ##STR18## were refluxed in 250 ml of toluene, 5.4 g of ethylene glycol and 2 drops of phosphoric acid for 5 hours. The reaction mixture was then filtered hot and the filtrate was cooled down. The precipitated dye of the formula ##STR19## was filtered off with suction and dried.

Yield: 3.4 g; melting point: 181° C.; λ_(max) (in acetone): 555 nm (ε=56000).

The same method gives the dyes listed in Tables 1 to 6, where the abbreviations have the following meanings:

Me=methyl

Et=ethyl

Pr=propyl

Ac=acetyl

    TABLE 1       ##STR20##        Ex.         No. Z.sup.1 /Z.sup.2 Z.sup.3 Z.sup.4 X Z.sup.5 Z.sup.6      Z.sup.7 Z.sup.8         4 Me/Me Cl H CCN NHAc H Et Et  5 CH.sub.2 CHCH.sub.2 OH Cl H CCN NHAc      H Et Et  6 CH.sub.2 CHCH.sub.2 OH Cl H CCN NHCOCH.sub.2 OCH.sub.3 H Et      Et  7 HOCH.sub.2 CHCHCH.sub.2 OH Cl H CCN NHCOCH.sub.2 OCH.sub.3 H Et Et       8 Me/Me Cl H N NHAc OEt C.sub.2 H.sub.4 CN CH.sub.2 CHCHCl  9 CH.sub.2      CHCH.sub.2 OH Cl H CCN NHCOEt H Bu Bu 10 Me/Me SO.sub.2 C.sub.6 H.sub.5      H CCN NHAc H Bu Bu 11 (CH.sub.2).sub.3 Cl H CCO.sub.2 Et OMe OMe C.sub.2      H.sub.4 OAc C.sub.2 H.sub.4 OAc 12 (CH.sub.2).sub.4 Cl H CCN Me H      C.sub.2 H.sub.4 OMe C.sub.2 H.sub.4 OMe 13 iso-Bu/iso-Bu Cl H CCN NHAc      OMe Et C.sub.2 H.sub.4 CN       14      ##STR21##       Cl H CCN NHAc OMe H CH.sub.2 CHCHCl       15      ##STR22##       Cl H CCN NHCOCH.sub.2 OCH.sub.3 H Bu Bu       16      ##STR23##       Cl H CCO.sub.2 Me NHCOCH.sub.2 OCH.sub.3 H Et Et  17 CH.sub.2       CHCH.sub.2 OH Cl H H NHAc OMe C.sub.2 H.sub.4 C.sub. 6 H.sub.5 C.sub.2      H.sub.4 OAc 18 Bu/Bu Cl H N NHAc OEt C.sub.2 H.sub.4 CN CH.sub.2      CHCH.sub.2 19 Pr/Pr Cl H N NHAc OMe CH.sub.2 CHCHCl CH.sub.2 CHCHCl 20      Et/Et Cl H N NHCOEt H C.sub.2 H.sub.4 OH C.sub.6       H.sub.5 21 (CH.sub.2).sub.2 OEt H CCN Me H Et C.sub.2 H.sub.4 CN 22      Me/Me CO.sub.2 Me H CCN NHAc OEt Et C.sub.2 H.sub.4 CO.sub.2 Me 23 Et/Et      C.sub.6 H.sub.5 H CCN NHAc OEt C.sub.2 H.sub.4 OAc C.sub.2 H.sub.4 CN 24      CH.sub.2 CHCH.sub.2 OH C.sub.6 H.sub.5 H CCN NHAc OEt C.sub.2 H.sub.4 CN      CH.sub.2 CHCH.sub.2 25 Me/Me 4-CH.sub.3 C.sub.6 H.sub.4 H CCN OEt OEt      C.sub.2 H.sub.4 OAc C.sub.2 H.sub.4 OAc 26 Et/Et Me H CCN NHAc H Et Et      27 Me/Me Cl CF.sub.3 CCN NHAc H Et Et 28 Pr/Pr C.sub.6 H.sub.5 H N NHAc      OMe C.sub.2 H.sub.4 CN CH.sub.2 CHCH.sub.2       29      ##STR24##       SC.sub.6 H.sub.5 H H NHAc OEt CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2      30 (CH.sub.2).sub.2 Me Me N NHAc OMe C.sub.2 H.sub.4 CN C.sub.2 H.sub.4      OAc       31      ##STR25##       Br H CCN Me H C.sub.2 H.sub.4 OH Et       32      ##STR26##       Br H N NHAc OMe CH.sub.2 CHCHCl CH.sub.2 CHCHCl  33 Et/Et OEt H CCN      NHAc OMe C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 CN 34 Pr/Pr C.sub.6 H.sub.5      H N H H C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 CO.sub.2 Me       35      ##STR27##       SO.sub.2 C.sub.2 H.sub.5 H N OEt OEt C.sub.2 H.sub.4 OAc C.sub.2      H.sub.4 OAc  36 Pr/Pr Me Me N H H Et Et 37 Et/Et 4-CH.sub.3 C.sub.6      H.sub.4 H CCN NHCOCH.sub.2 OCH.sub.3 H Bu Bu 38 Me/Me H H CCN NHAc H      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OAc Et 39 Et/Et SC.sub.6 H.sub.5 H CCN      NHAc OMe C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OAc Bu 40 Me/Me CO.sub.2 Et H  C      CN NHCOEt OMe Pr Pr

                                      TABLE 2     __________________________________________________________________________      ##STR28##     Ex.     No.        Z.sup.1 /Z.sup.2                   Z.sup.3                      Z.sup.4                        X    Z.sup.5                                    Z.sup.6                                       Z.sup.7     __________________________________________________________________________     41 CH.sub.2 CHCH.sub.2 OH                   Cl H CCN  Thien-2-yl                                    Et Et     42 Me/Me      Cl H CCN  C.sub.6 H.sub.5                                    Et Et     43 Pr/Pr      OEt                      H CCN  Thien-3-yl                                    Bu Bu     44 Et/Et      C.sub.6 H.sub.5                      H CCN  iso-Pr Bu Bu     45 (CH.sub.2).sub.2                   Cl H N    Et     Et Et     46 Me/Me      Cl H N    C.sub.6 H.sub.5                                    Et Et     __________________________________________________________________________

                                      TABLE 3     __________________________________________________________________________      ##STR29##     Ex.     No.        Z.sup.1 /Z.sup.2   Z.sup.3                               Z.sup.4                                 X     Z.sup.5                                             Z.sup.6                                                   Z.sup.7                                                     Z.sup.8     __________________________________________________________________________     47 (CH.sub.2).sub.2   Cl  H CCN   Et    Et    H C.sub.2 H.sub.4 C.sub.6                                                     H.sub.5     48 CH.sub.2 CHCH.sub.2 OH                           Cl  H N     C.sub.2 H.sub.4 OMe                                             C.sub.2 H.sub.4 OMe                                                   H C.sub.3 H.sub.6 OMe     49 CH.sub.2 CHCH.sub.2 OH                           C.sub.6 H.sub.5                               H CCN   Et    Et    H C.sub.3 H.sub.6 OC.sub. 2                                                     H.sub.4 OC.sub.6 H.sub.5     50 Me/Me              SC.sub.6 H.sub.5                               H N     C.sub.2 H.sub.4 OMe                                             C.sub.2 H.sub.4 OMe                                                   H Et     51 Pr/Pr              Cl  H CCO.sub.2 Et                                       C.sub.2 H.sub.4 OMe                                             C.sub.2 H.sub.4 OMe                                                   H CH.sub.2 CHCH.sub.2     52 C.sub.2 H.sub.4 SO.sub.3 Na/C.sub.2 H.sub.4 SO.sub.3 Na                           Cl  H CCN   Et    Et    H C.sub.3 H.sub.6 OEt     53         ##STR30##         Cl  H CCN   Et    C.sub.3 H.sub.6 OMe                                                   H C.sub.3 H.sub.6 OMe     54         ##STR31##         Cl  H CCN   Et    Et    H Et     __________________________________________________________________________

                                      TABLE 4     __________________________________________________________________________      ##STR32##     Ex.     No.        Z.sup.1 /Z.sup.2                   Z.sup.3                       Z.sup.4                          X    Z.sup.5                                  Z.sup.6                                     Z.sup.7     __________________________________________________________________________     55 Me/Me      Cl  H  CCN  H  NH.sub.2                                     C.sub.6 H.sub.5     56 CH.sub.2 CHCH.sub.2 OH                   Cl  H  N    H  OH C.sub.6 H.sub.5     57 Et/Et      C.sub.6 H.sub.5                       H  CCN  Me NH.sub.2                                     C.sub.6 H.sub.5     58 Pr/Pr      Cl  CF.sub.3                          CCN  H  NH.sub.2                                     C.sub.6 H.sub.5 CH.sub.2     59 Me/Me      SC.sub.6 H.sub.5                       H  N    H  NH.sub.2                                     C.sub.6 H.sub.5     60 Pr/Pr      CO.sub.2 Et                       H  C CN H  NH.sub.2                                     C.sub.6 H.sub.5 CH.sub.2     61 (CH.sub.2).sub.2                   OEt H  CCN  Me NH.sub.2                                     C.sub.6 H.sub.5     __________________________________________________________________________

                                      TABLE 5     __________________________________________________________________________      ##STR33##     Ex.     No.        Z.sup.1 /Z.sup.2  Z.sup.3                             Z.sup.4                                X    Z.sup.5     __________________________________________________________________________     62 Me/Me             OEt                             H  CCN  Et     63 Pr/Pr             Cl H  CCN  C.sub.6 H.sub.5     64 (CH.sub.2).sub.2  Br H  CCN  CH.sub.2 C.sub.6 H.sub.5     65         ##STR34##        Cl H  N    C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5     66 CH.sub.2 CHCH.sub.2 OH                          C.sub.6 H.sub.5                             H  CCN  Pr     67         ##STR35##        CH.sub.3                             H  CCN  Me     68 Et/Et             CH.sub.3                             CH.sub.3                                N    Me     __________________________________________________________________________

                                      TABLE 6     __________________________________________________________________________      ##STR36##     Ex.     No.        Z.sup.1 /Z.sup.2              Z.sup.3                 Z.sup.4                    X     Z.sup.5     Z.sup.6     __________________________________________________________________________     69 CH.sub.2 CH.sub.2              Cl H  CCN                           ##STR37##  Me     70 Me/Me Cl H  CCN                           ##STR38##  Me     71 Me/Me Cl H  N                           ##STR39##  Me     72 Me/Me Cl H  N     CH.sub.2 CH.sub.2 CO.sub.2 Me                                      Me     73 CH.sub.2 CH.sub.2              Cl H  CCN   CH.sub.2 CH.sub.2 CN                                      Me     74 CH.sub.2 CH.sub.2              Cl H  CCN   CH.sub.2 CH.sub.2 OEt                                      Me     __________________________________________________________________________

EXAMPLE 75

10 g of the dye of Example 1 were stirred for 1 hour with 20 ml of tetrahydrofuran and 100 ml of 10% strength by weight sulfuric acid with heating to 60° C. Thereafter the mixture was cooled with ice and filtered with suction, and the filter residue was dried under reduced pressure.

This yielded 9.5 g of the dye of the formula ##STR40## in a novel crystal form which has the following X-ray diffraction diagram: lines of high intensity at diffraction angles Θ °! of 8.497 and 9.175;

lines of medium intensity at diffraction angles Θ °! of 7.018, 11.836 and 9.721;

lines of low intensity at diffraction angles Θ °! of 25.164, 5.920, 25.934, 24.425, 23.442, 26.335, 13.119, 17.906, 15.674, 13.963, 15.153, 27.471, 14.630, 17.028, 18.833, 20.982, 28.275, 21.247, 19.490, 29.898, 30.726 and 34.570.

EXAMPLE 76

10 g of the dye of Example 2 were stirred for 1 hour with 20 ml of tetrahydrofuran and 100 ml of 10% strength by weight sulfuric acid with heating to 60° C. Thereafter the mixture was cooled down with ice and filtered with suction and the filter residue was dried under reduced pressure.

This yielded 9.2 g of the dye of the formula ##STR41## in a novel crystal form which has the following X-ray diffraction diagram: lines of high intensity at diffraction angles Θ °! of 24.971 and 12.551;

lines of medium intensity at diffraction angles Θ °! of 22.850 and 11.093;

lines of low intensity at diffraction angles Θ °! of 11.548, 9.100, 27.564, 29.233, 17.967, 7.424, 22.255, 30.296, 28.175, 13.645, 14.406, 17.368, 26.458, 16.018, 16.809, 19.206, 20.006, 32.464, 34.775, 33.479 and 33.833.

EXAMPLE 77

10 g of the dye of Example 3 were stirred for 1 hour with 20 ml of tetrahydrofuran and 100 ml of 10% strength by weight sulfuric acid with heating to 60° C. Thereafter the mixture was cooled down with ice and filtered with suction and the filter residue was dried under reduced pressure.

This yielded 9.7 g of the dye of the formula ##STR42## in a novel crystal form which has the following X-ray diffraction diagram: lines of high intensity at diffraction angles Θ °! of 7.441;

lines of medium intensity at diffraction angles Θ °! of 11.090;

lines of low intensity at diffraction angles Θ °! of 8.662, 10.063, 26.181, 17.373, 19.540, 22.901, 14.950, 12.888, 14.097, 15.961, 28.237, 27.752, 29.035, 32.108, 34.326, 33.239 and 33.543. 

We claim
 1. A crystal form for each of the dyes of the formulae ##STR43## which crystal forms have the following X-ray diffraction diagrams (Cu--K_(g) radiation):IIIa)lines of high intensity at diffraction angles Θ °! of 8.497 and 9.175; lines of medium intensity at diffraction angles Θ °! of 7.018, 11.836 and 9.721; lines of low intensity at diffraction angles Θ °! of 25.164, 5.920, 25.934, 24.425, 23.442, 26.335, 13.119, 17.906, 15.674, 13.963, 15.153, 27.471, 14.630, 17.028, 18.833, 20.982, 28.275, 21.247, 19.490, 29.898, 30.726 and 34.570; IIIb)lines of high intensity at diffraction angles Θ °! of 24.971 and 12.551; lines of medium intensity at diffraction angles Θ °! of 22.850 and 11.093; lines of low intensity at diffraction angles Θ °! of 11.548, 9.100, 27.564, 29.233, 17.967, 7.424, 22.255, 30.296, 28.175, 13.645, 14.406, 17.368, 26.458, 16.018, 16.809, 19.206, 20.006, 32.464, 34.775, 33.479 and 33.833; IIIc)lines of high intensity at diffraction angles Θ °! of 7.441; lines of medium intensity at diffraction angles Θ °! of 11.090; lines of low intensity at diffraction angles Θ °! of 8.662, 10.063, 26.181, 17.373, 19.540, 22.901, 14.950, 12.888, 14.C97, 15.961, 28.237, 27.752, 29.035, 32.108, 34.326, 33.239 and 33.543. 